Anthraquinone-benzacridone vat dyestuffs



Patented Oct. 26, 1937 ANTHRAQUINONE-BENZAC V DYES-TUFFS RIDQNEI vli'r Wilhelm Bauer, Leverkusen wiesdorhand Hans Hoyer and Bernhard Bollweg, Leverkusen-I. G.

Werk, Germany, Works, 1110- -])ela.wareW-,

No. 80,634. In Germany1-May'23Q1935 4 Claims. (o1.:26of'-3'7) "The present invention relates to new vat dyestuffs of the anthraquinone series.

The anthraquinone-2.1(N)-benzacridones are vat dyestuffs which are distinguished by an excel- 5 lent fastness to light and yield red to bluish-red shades.' However, most of these compounds cannot be employed for practical purposes owing to their insufficient fastness to boiling. It is known that the fastness to boiling of these products can be improved to acertain extent by the introductionof halogen substituents; however, no clear successhas been reached up to the present time, ,It is the object of our present invention to prepare anthraquinone-benzacridones which as to 15 fastness properties meet every practical demand. Another object of our invention resides in the de velopment of a process by which anthraquinonebenzacridones of the required fastness properties can be prepared. With these and other objects 20, in View our invention primarily consists in the preparation of new vat dyestuffs which are defined as anthraquinone-2.1. (N) -1'.2- (N) -benzacridones which contain an aryloxy group in 3'position. These compounds combine a good R=Ol or No,

fastness to light with an excellent fastness to boil a assignors to. General Aniline New York, N y a corporation of No Drawing. "Application May-19,

ing. They yield clear violet toured shades. The presence of indifierent substituents in the benzacridone as well as in the aryloxy group is not precluded-halogen preferredsubstituents;

atoms or For the preparation of our new vat dyestufis we, start from 2'-ary1oxy-l-phenylaminoanthraqui-.

none'i-2-carboxylic acids tives thereof.

or the functional deriva- These compounds may contain in-;v

different substitutents providedthat the Bz -6.-' position is unsubstituted. Upon the action of ring closing agents minium chloride'or such as benzoyl chloride, alu-.

ferric chloride therdesired vat dyestufis are obtained in'a good yield. Thev2 aryloxy-l-phenylaminoanthraquinone- 2 -carbox- OFFICE i4 alkoxy groups being 5 ylic 'acids.- may easily be obtained by causing ortho-aminodiaryl ethers toreact upon l-chloro. oi" 1 -nitroanthraquinone-2-carboxylic acids. As examples'for' functional derivatives of the carbocylic acids described there many be mentioned their esters,

chlorides or nitriles.

The formation of thejnewfdyestuffs probably corresponds to the following equation:

tion,irinse.d and dried. The dyestuff: tormsviolete fastness. e

' I ExampleZ I I Parts by weight l-nitroanthr'aquinone-2+carboxylic. acid 29.7 .Ortho-aminophenylether 37 OrthodichlorobenZene ;.L 206 addition of 30 parts by volume of w sulfuric a,cid.- They dye vegetable fibresfrom a 2 f I. p

' The following examples illustrate the invention without, however, restricting it thereto.

Example 1 Parts by weight 1 chloroanthraquinone 2 carboxylic acid methylester Ortho-aminodiphenylether- Anhydrous sodium acetate Copper acetate ii The reaction product is saponififld by heating for 1 hour with 200 parts by volume of'alcohol, 200 parts by volume of water, 50 parts by volume of pyridine and 35 parts by volume of a. 33%. sodium hydroxide lye. Thereupon the-solution is filtered and the 2-phenoxy-l-phenylamin'oanthraquir none-2-carboxylic acid which'is of jviolet coloration is precipitated. The product is filtered with suction, rinsed and dried; byhea'tirigit fQIZ'l hcur 1; a and a half to C. with 40 arts byiweight' of benzoyl chloride and 200 parts by volume of. 011-. thodichlorobenzene the acridone is formedwhich I alreadysepar ates while hot in a crystalline-.fcrm..

After cooling, the1precipitate isifiltered with sucblackneedles which dissolve with a yellow-red color in .cold concentrated sulfuric-acid. .On dilution with water this solution precipitates in violet. flakes. The dyestufi: may be. recrystallized from hot. 'nitrobenzene- From a. violet vat the; dyestufi dyes vegetable fibres in. fast violet. shades and is suitableior the-sodiumiormaldeh-yde sulfoxylate, printing process; Furthermore, it-maybe%transf.orrned inz the usual manner into its leuco. sulfuric. .acid esters whichyield in the dyeing and-printinQprocess violetishadesoi good are heated m2 hoursto. 1.75? CJvia'ter formed during the reaction'bei ngfdistill'ed bfia. 33% sodium hydroxide lye and some water the orthodichlorobenzene is blownoil: with steam. Thereupon the solution is filteredand the product precipitated by means 01 acetic acid; the precipitate is rinsed .and dried. The product is transformed as described in Example liinto theacridone which may bepurified, if necessary,:by recrystallization from nitrobenzene. The dyestuff forms violet needles which dissolve with a .yellowishred color incold.

violet vat in a similar violet shadeto the dyestufi of Example 1;. Example 3 -1 chloroanthraquinone 2 carboxylic acid methylester "'30 5-chloro-2-amino-diphenylether; 30 Anhydrous sodiumacetateaufln; 9 Copper acetate Q are heated whilst stirring for two hours: to -170 C. The warm molten mass having beeng diluted with 200 parts by volume oialcoholibd parts by volume of pyridine, 200 parts by volume of water and 35 parts by volume of a 35% sodium benzene and heated with I a benzoyl' chloride tot-.1150. C..,f;the;acridone already crystallizin'g'out tosome'"extenv'at elevated temare heated whilst stirring for 2'hours to fll ifi f lfuric. a id. v yields; bluish'violet shades of good fastness propa s y weight peraturesi The dyestuff forms brown-red neewhich dissolve with a crimson red color in From a violet vat the acridone erties Example 4 Parts by weight .I-chloroanthraquinonee2-carboxylic acid--- 30 4.6-dichloro-2-aminodiphenylether 30 Anhydrous sodium acetate; 9 Gopher acetate are condensed in the manner described in the preced ng example. The arrthraquinone-ZJ-(Nl- 1 .2 ((N) -4 -6' -dichl,oro-3' -phenoxybenzene, acridone is thus obtained. The dyestufi iorms red 7 leaflets. which dissolve in sulfuric acid witha goldenryellow color. 7 The acridone yields from a violet vat, clear bluish-pink shades of; excellent fastness,v

Example 5."

In this example-"we confine ourselves to the 35 drawing of the for u1ae;of several further dyestuffs or the character described. 'Allthese prod-- ucts canbe prepared in a mannerquite analogous to that described in the-foregoing examples. The; right hand column shows the'shades of the dye-: stu-fisin question;

reddish-violet bluish-pink EN 0 reddish-violet EN O bluish-red I G O Cl HN violet O I C O 0 EN bluish-violet I O pink EN 0 bluish-pink EN 0 yellowish-pink HN pink 0 violet 1. -Anthraquinone-2.1(N) 1'.2(N) benzacridones which contain in 3'-position an aryloxy radical selected from the group consisting of phenoxy and naphthyloxy radicals.

2. The anthraquinone 2.1(N) 1'.2'(N) 3' phenoxy-benzacridone.

3. The anthraquinone 2.1(N) 1.2'(N) 3 phenoxy-benzacridones which contain halogen atoms in the acridone-Bz-nucleus.

4. Theanthraquinone 2.1(N) 12'(N) L 3' phenoxy-4'.6-dichloro-benzacridone.

WILHELM BAUER. HANS HOYER. BERNHARD BOLLWEG. 

